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acid with soda.

' 8 UNITED STATES PATENT @FFICEQI PHILIPP OTT, 0E ELBERFELD, PRUSSIA, GERMANY, Asslenon TO THE ,EAE NEABRIKEN, voR AI-is FR. BAYER & 00., OF sAME PLACE.

AZO DYE.

SPECIFICATION forming part of Letters Patent No. 423,569, dated March 18, 1890.

Application filed September 12, 1889. Serial No. 323,742. (Specimens) Patented in England May 3, 1889, No. 7,314, and May 9,1889, No. 7,802, and in France May 3,1889,N0.184,799.

7,314, and May 9, 1889, No. 7,802, and in France May 3, 1889, Nol'184:,799;) and I do hereby declare the following to be a full, clear, andexact description of the invention, such as will enable others skilled in the art towhich itappertains to make and use the same.

The invention relates to the production of substantive dyes, and more especially to the production of such dyes from diamidodiphenylene oxide and diamidoditoluylene oxide. I have discovered that these diamines can be readily obtained by melting ortho-benzidine disulphoacid and ortho-tolidine disulpho- These paradiamines form soluble tetrazo compounds that will react with two molecules of an amine or phenol, or their sulpho or carbo or their sulpho-carbo acids, and will form. new dye-stufis like the tetrazocompoundsof benzidine, tolidine, (inc,

By combining theftetrazo compounds of diamidodiphenylene.oxide and diamidoditoluylene oxide with two molecules of an amine, or a phenol or their sulpho or carbo acids or their sulpho-carbo acids, the dye-stuff is produced at once; butif these tetrazo compounds are combined with one molecule only intermediate products are obtained that are not dye-stuffs, but that can be converted into suchby combining them with another mole-- differ greatly from the dye-suffs derived from finer and bluer shades.

In carrying out my invention I proceed as benzidine and .tolidine, in that they are of follows; Diamidodiphenylene oxide and diamidoditoluylene oxide are diazotized in a hydrochloric-acid solution containing the theoretical quantity ofsodium nitrite. The resultingtetrazo compounds are allowed to flow into two molecules of an amine or phenol or their sulpho or carbo or sulpho-carbo acids, the amides being coupled in an acetic-acid solution and the phenols in an alkaline solution. The product of the coupling with an amine is allowed to stand for some time, the reaction being finally completed by heating to about 80 centigrade, after which it is neutralized with soda-lye and the dye-stuff salted out. The phenol dye-studs, on the other hand, form immediately, and are isolated by treatment with common salt, in a well-known manner, and dried.

In order to obtain mixed dye-stuffs, one

molecule of the tetrazo compound of diamidodiphenylene oxide or diamidoditoluylene oxide is caused to react upon one molecule of an amine or phenol or the sulpho or carbo or sulpho-carbo acids thereof in an acetic-acid solution. The intermediate product formed is combined with one molecule of any other amineor phenol or their sulpho or carbo or sulphogcarbo'acids, the amines being likewise coupled in an acetic-acid solution and the phenols in an alkaline solution and treated as above set forth.

no sulpho or carbo acid group, dye-stuffs are obtained by the above -described process, which are insoluble in water and are rendered soluble by sulphonation. To this end one part of the dye-stuff'is introduced into three parts, by weight, of fuming sulphuric acid and the resulting melt allowed to stand until it is found on trial to readily dissolve in alkaline Water. The melt is then poured on ice and the separated dye-stuff acid converted into dye-stuff by'dissolving in alkali.

The following examples will more clearly show the manner of carrying out my invention.

Dye 7 stuffy-0m diamtdodt'phenylene oxide and two molecules of alpha-naphthylam'me. I add to a solution of twenty-live kilograms of alphamaphthylamine in hydrochloric acid quantity of a solution of sodium nitrite to flow into the hydrochloric-acid solution of the diamidodiphenylene oxide. By the addition of acetate of soda to the tetraz'o compound the formation of the dye-stuff takes place. After standing for twelve hours the temperature is raised to about 80 centigrade, and the mixture is acidulated and filtered off. The dye-stuff thus obtained dissolves in alcohol with a bluish-red color. In orderto render this dye-stuff soluble, ten parts, by weight, are combined with thirty p'arts, by

weight, of fuming sulphuric acid containing twenty per oentum of anhydrous acid of about to centi'grade, and the melt is allowed to stand until it is found on test tov dissolve readily in alkaline Water. The melt is then poured on ice j and the separated dye-stuff acid filtered on and converted into dye-stuff by Solution in an alkaline lye. I From this the dye stufli .is isolated by means of common salt. It dyes cotton a bluish-red.

Dy'e-stufi from cllol'nticlocllphen'yleue oxide and two molecules of alpha-naphthylam iuef Monosulpho aclcl-A solution of the tetraz'o compound of diamidodiphenyleneoxide, corresponding to ten kilograms of nitrite, is

eombinedwith an acetic-acid solution of for-- ty 3 five kilogramsv of alpha naphthylamine monosulpho-acid. After standing for twenty four hours the mixture is heated to 80 cengrade and alkalinized by the addition'of soda lye. It is then salted out, filtered, and dried. The dye-stuff also dyes cotton a bluish-red. v

Dye sltufi from cliamz'doditoluylene oxide 1 and two molecules of alpha-naphthol mon'os-uljoho' a cicl.Thje tetrazo'compound of the diamidodito'luylene oxide, obtained in the same manner as that of the diamidodiphehylene.

. oxide and corresponding to ten kilograms of sodium nitrite, is poured into a solution of forty kilos alpha-naphthol monosulp'ho-acid and kept alkaline by means of carbonate of sodium, and the dye-stuff is salted out. It dyes cotton violet.

Dye stu f from clt'omt'clocllphenylene oxide and one molecule ofalp ha-uapthol more osulphoacid and one molecule of ctlpha-uaphlhylamine monosulpho-acicl.The tetrazo compound of the diamidodiphenylene oxide containing ten parts, by weight, of sodium nitrite, is caused to flow into an acetic-acid solution of sixteen parts, by Weight, of alpha-naphthylamine monosulpho-acid. After standing for three 'or four hours an intermediate product is formed, which is then introduced into an alkaline solution of twenty-"five parts, by

Weight, of alpha-naphthol monosulp'ho-aoid.

The dye-stuff forms at once and is separated by filtration and dried. It dyes cotton direct with a Bordeaux-like color.

Dye-Stu from cliamlcloclitoluylene ooticle and one mo ecule of alpha-no. hlylamute monosulpho-ac'icl and one molecu' e of resorclur ln this case the tetrazo compound of diamidodiphenylene oxide of the preceding example is replaced'by a corresponding quantity of the tetra-Z0 compound of diamidoditoluylene oxide, and the intermediate product, diamidoclitoluylene oxide and one molecule of alphanapht'hylamine inonosulp'ho acid obtained, which is introduced into an alkaline solution of twenty-five kilos of resorci-ni, and a fine red dye-stuff is obtained.

I Having described my invention, what I claim, and "desire to secure by Letters Patent; is-- 1. The herein-described process of obtaining substantive dye stu ffs' from diamidodip'henylene oxide and from diamidoditoluylene oxide, which consists in combining one molecule of their tetra'zo compounds withtwo acids. 7

2. The herein-described rocess-0f obtaining substantive dye-stuffs from intermediate products not dye-stuffs in themselvespderived from diamidodiphenyl'ene oxide and from diamidoditoluylene oxidegwhich consists in combining thetetra'zo compounds of the latter with one molecule of an amine or a phenol,'o"r their sulpho or carbo or theii'sulpho-carbo acids, and combining the product of the reaction with another molecule of an amine or a phenol oritheir sulpho or carbo acids or their sulphoca rbo acids. H r

In testimony whereof I affix my signature in presence of two witnesses. H I V L PHILIPP OTT. Witnesses: CARL KRIEGER, CARL DUNSBERG.

, 5 1 molecules of an amine or phenolor their 

